Nickel-titanium-yttrium alloys with reduced oxide inclusions

ABSTRACT

A nickel-titanium alloy is made to be wholly or substantially free of titanium-rich oxide inclusions by including yttrium in an amount up to 0.15 wt. %, with the balance of the alloy being nickel and titanium in approximately equal proportion. For example, a NiTiY alloy may have a composition including, in weight percent based on total alloy weight: between 50 and 60 wt. % nickel; between 40 and 50 wt. % titanium; and between 0.01 and 0.15 wt. % yttrium. The resulting alloy is capable of being drawn into various forms, e.g., fine medical-grade wire, without exhibiting an unacceptable tendency to develop surface defects or to fracture or crack during cold drawing or forging. The resulting final forms exhibit favorable fatigue strength and fatigue-resistant characteristics.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit under Title 35, U.S.C. § 119(e) ofU.S. Provisional Patent Application Ser. No. 62/325,283, entitledNICKEL-TITANIUM-YTTRIUM ALLOYS WITH REDUCED OXIDE INCLUSIONS and filedon Apr. 20, 2016, the entire disclosure of which is hereby expresslyincorporated by reference herein.

BACKGROUND 1. Technical Field

The present disclosure is directed to shape-memory alloys and methods ofmaking the same, and in particular, to nickel-titanium shape-memoryalloys with enhanced fatigue performance.

2. Description of the Related Art

Specialized alloys have been developed for surgical implantapplications. One such alloy, known as Nitinol (also commonly referredto as “NiTi”), is produced in bar and wire forms intended for use insurgical implants such as, for example, stents and pacing leads adaptedto relay a cardiac pacing pulse from an implanted defibrillator orpacing device to the heart. NiTi and similar ternary, quaternary, andquinary alloys are also envisioned for use as actuators, or solid statethermal motors that can be used to replace motors for axial, flexural,or rotary motion in automotive, aerospace and medical devices andmachines.

Standard specifications and chemistry for wrought NiTi alloy for use insurgical implant applications may be found in ASTM F2063, the entiredisclosure of which is hereby incorporated herein by reference. Amaterial constituency for materials made in accordance with ASTM F2063is shown below as Table 1.

TABLE 1 Chemical Composition Requirements % (mass/ Element mass) Nickel54.5 to 57.0 Carbon, maximum 0.050 Cobalt, maximum 0.050 Copper, maximum0.010 Chromium, maximum 0.010 Hydrogen, maximum 0.005 Iron, maximum0.050 Niobium, maximum 0.025 Nitrogen plus Oxygen, maximum 0.050Titanium^(A) Balance ^(A)Approximately equal to the difference between100% and the sum percentage of the other specified elements. Thepercentage titanium content by difference is not required to bereported.

In some cases, the fatigue performance of NiTi alloys may be limited byinclusions (shown in FIG. 1A, which are drawn to scale according toscale 9) such as oxides and carbides which are formed during melting andsolidification. Carbides are relatively small in size, and are generallyformed due to carbon contamination from the graphite crucible used inthe Vacuum Induction Melt (VIM). By contrast, oxides are normallysubstantially larger than carbides in the as-cast condition. Oxides maybreak up during processing (e.g., during hot forming or cold formingprocesses) to form stringers. FIG. 1A shows the microstructure of aningot 1 formed of a binary NiTi alloy at a magnification such that theillustrated scale in the lower-right hand corner of the imagecorresponds to 20 μm. As shown in the image of FIG. 1A, inclusions 5 areformed within the microstructure 3 of the alloy, and may contribute tothe formation of stringers when the alloy is processed.

Known methods for reducing the fraction of the oxide include usinghigher purity raw material, zone refinement, high-energy re-melting suchas plasma or electron beam methods, and using a high vacuum (i.e.greater multiples lower than atmospheric pressure) during ingot meltingand solidification. Methods that employ combinations of high purity rawmetals and/or high energy melting, including high-vacuum methods, areexpensive and not practically attractive due to high energy consumptionand associated high production costs. Other oxide-reduction methods suchas those described above also involve high input costs and/or lowprocess yields.

What is needed is an improvement over the foregoing.

SUMMARY

The present disclosure is directed to a nickel-titanium alloy made to bewholly or substantially free of titanium-rich oxide inclusions byincluding yttrium in an amount up to 0.15 wt. %, with the balance of thealloy being nickel and titanium in approximately equal proportion. Forexample, a NiTiY alloy may have a composition including, in weightpercent based on total alloy weight: between 50 wt. % and 60 wt. %nickel; between 0.01 and 0.15 wt. % yttrium; and balance titanium. Theresulting alloy is capable of being drawn into various forms, e.g., finemedical-grade wire, without exhibiting an unacceptable tendency todevelop surface defects or to fracture or crack during cold drawing orforging. The resulting final forms exhibit favorable fatigue strengthand fatigue-resistant characteristics.

The present disclosure is further directed to articles of manufactureincluding any of the novel alloys described herein. Examples of sucharticles of manufacture include a bar, a wire, a tube, a surgicalimplant device, a component for a surgical implant device, animplantable defibrillator, a component for an implantable defibrillator,an implantable pace maker, a component for an implantable pacemaker, apacing lead, and a vascular or non-vascular stent. In instances wherethe article of manufacture is a bar or a wire, the article also may beone qualified for use in surgical implant applications under ASTMstandard specification F2063.

The present disclosure is additionally directed to a method of making analloy, wherein the method includes preparing an ingot having thechemistry set forth above. In certain embodiments of the method, theingot is wholly or substantially free of carbide and titanium-rich oxideinclusions. The method may also include processing the ingot into one ofa bar, a wire, and a tube, which may be further processed into anarticle of manufacture as described herein.

In one form thereof, the present disclosure provides a nickel-titanium(NiTi) alloy, comprising: between 50 wt. % nickel and 60 wt. % nickel;between 40 wt. % titanium and 50 wt. % titanium; and between 0.01 wt. %yttrium and 0.15 wt. % yttrium.

In another form thereof, the present disclosure provides anickel-titanium (NiTi) alloy, comprising: at least 20 wt. % nickel;between 35 wt. % titanium and 55 wt. % titanium; between 0.01 wt. %yttrium and 0.15 wt. % yttrium; and at least one of: copper between 1wt. % and 10 wt. %, in lieu of an equal amount of nickel; niobiumbetween 1 wt. % and 15 wt. %, in lieu of an equal amount of titanium;hafnium between 0.5 wt. % and 50 wt. %, in lieu of an equal amount oftitanium; zirconium between 0.5 wt. % and 35 wt. %, in lieu of an equalamount of titanium; cobalt between 0.1 wt. % and 5 wt. %, in lieu of anequal amount of titanium, nickel, or a combination of titanium andnickel; chromium between 0.1 wt. % and 1 wt. %, in lieu of an equalamount of titanium; and iron between 0.1 wt. % and 10 wt. %, in lieu ofan equal amount of titanium, nickel, or a combination of titanium andnickel.

In yet another form thereof, the present disclosure provides a method ofmaking a nickel-titanium (NiTi) alloy, comprising: providing between 50wt. % nickel and 60 wt. % nickel; providing between 40 wt. % titaniumand 50 wt. % titanium; providing between 0.01 wt. % yttrium and 0.15 wt.% yttrium; and forming an ingot including the nickel, the titanium andthe yttrium.

In still another form thereof, the present disclosure provides a methodof making a nickel-titanium (NiTi) alloy, comprising: providing at least20 wt. % nickel; providing between 35 wt. % titanium and 55 wt. %titanium; providing between 0.01 wt. % yttrium and 0.15 wt. % yttrium;providing at least one of an additional element; and forming an ingotincluding the nickel, the titanium and the yttrium, the ingot furtherincluding at least one of the copper, the niobium, the hafnium, thezirconium, the cobalt, the chromium and the iron. The additionalelements may be any of the following: copper between 1 wt. % and 10 wt.%, in lieu of an equal amount of nickel; niobium between 1 wt. % and 15wt. %, in lieu of an equal amount of titanium; hafnium between 0.5 wt. %and 50 wt. %, in lieu of an equal amount of titanium; zirconium between0.5 wt. % and 35 wt. %, in lieu of an equal amount of titanium; cobaltbetween 0.1 wt. % and 5 wt. %, in lieu of an equal amount of titanium,nickel, or a combination of titanium and nickel; chromium between 0.1wt. % and 1 wt. %, in lieu of an equal amount of titanium; and ironbetween 0.1 wt. % and 10 wt. %, in lieu of an equal amount of titanium,nickel, or a combination of titanium and nickel.

BRIEF DESCRIPTION OF THE DRAWINGS

The above mentioned and other features and objects of this invention,and the manner of attaining them, will become more apparent and theinvention itself will be better understood by reference to the followingdescription of embodiments of the invention taken in conjunction withthe accompanying drawings, wherein:

FIG. 1A is an image of an ingot of a known NiTi alloy in an as-castcondition, in which the ingot and its associated microstructuralfeatures are shown to scale according to the illustrated scale inmicrometers in the bottom right hand corner of the figure;

FIG. 1B is an image of an ingot of a NiTiY alloy made in accordance withthe present disclosure with 0.04 wt. % yttrium in an as-cast condition,in which the ingot and its associated microstructural features are shownto scale according to the illustrated scale in micrometers in the bottomright hand corner of the figure;

FIG. 2A is an image of an ingot of another NiTiY alloy made inaccordance with the present disclosure with 0.01 wt. % yttrium in anas-cast condition, in which the ingot and its associated microstructuralfeatures are shown to scale according to the illustrated scale inmicrometers in the bottom right hand corner of the figure;

FIG. 2B is an image of an ingot of another NiTiY alloy made inaccordance with the present disclosure with 0.02 wt. % yttrium in anas-cast condition, in which the ingot and its associated microstructuralfeatures are shown to scale according to the illustrated scale inmicrometers in the bottom right hand corner of the figure;

FIG. 2C is an image of an ingot of another NiTiY alloy made inaccordance with the present disclosure with 0.16 wt. % yttrium in anas-cast condition, in which the ingot and its associated microstructuralfeatures are shown to scale according to the illustrated scale inmicrometers in the bottom right hand corner of the figure;

FIG. 2D is an image of an ingot of another NiTiY alloy made inaccordance with the present disclosure with 0.3 wt. % yttrium in anas-cast condition, in which the ingot and its associated microstructuralfeatures are shown to scale according to the illustrated scale inmicrometers in the bottom right hand corner of the figure;

FIG. 3A is an image of an ingot of a NiTiNb alloy in an as-castcondition, in which the ingot and its associated microstructuralfeatures are shown to scale according to the illustrated scale inmicrometers in the bottom right hand corner of the figure;

FIG. 3B is an image of a microstructure of a NiTiNb alloy made inaccordance with the present disclosure, with 0.1 wt. % yttrium in anas-cast condition, in which the ingot and its associated microstructuralfeatures are shown to scale according to the illustrated scale inmicrometers in the bottom right hand corner of the figure;

FIG. 4 is an image of a portion of a longitudinal cross section of theNiTiY alloy of FIG. 2B, in which the features of the wire are shown toscale according to the illustrated scale in micrometers in the bottomright hand corner of the figure;

FIG. 5 is an image showing a fracture face after fatigue testing for2,996,258 cycles in a sample of the NiTiY alloy of FIG. 4, in which thefeatures of the wire are shown to scale according to the illustratedscale in micrometers in the bottom right hand corner of the figure;

FIG. 6 is an elevation view illustrating the geometry of a braided stenthaving diameter D_(S), the stent comprising wire elements formed into amesh tubular scaffold, in accordance with the present disclosure;

FIG. 7A is a schematic view illustrating an exemplary forming process ofmonolithic wire using a lubricated drawing die;

FIG. 7B is a schematic view illustrating an exemplary forming process ofcomposite wire using a lubricated drawing die;

FIG. 7C is an elevation view of a wire in accordance with the presentdisclosure, before a final cold working process; and

FIG. 7D is an elevation view of the wire of FIG. 7C, after the finalcold working process.

Corresponding reference characters indicate corresponding partsthroughout the several views. Although the exemplifications set outherein illustrate embodiments of the invention, the embodimentsdisclosed below are not intended to be exhaustive or to be construed aslimiting the scope of the invention to the precise form disclosed.

DETAILED DESCRIPTION Introduction

The alloy of the present disclosure is a nickel-titanium-yttrium (NiTiY)alloy that, in certain embodiments, exhibits significantly improvedproperties depending on the specific concentration of yttrium present inthe alloy. For example, the present NiTiY alloys having only a small(e.g., less than 0.15 wt. %) amount of yttrium exhibit improved fatigueresistance relative to conventional NiTi alloys and benefit from asignificantly lower fracture rate compared to conventional NiTi alloys,particularly when the alloy is in the form of a fine drawn wire with asmall diameter as may be desired for use in pacing leads and certainother surgical implant applications.

Terminology

As used herein, “wire” or “wire product” encompasses continuous wire andwire products which may be continuously produced and wound onto a spoolfor later dispensation and use, such as wire having a round crosssection and wire having a non-round cross section, including flat wireor ribbon. “Wire” or “wire product” also encompasses other wire-basedproducts such as strands, cables, coil, and tubing, which may beproduced at a particular length depending on a particular application.In some exemplary embodiments, a wire or wire product in accordance withthe present disclosure may have a diameter up to 2.5 mm. In addition towire and wire products, the principles of the present disclosure can beused to manufacture other material forms such as rod materials having adiameter greater than 2.5 mm up to 20 mm. Thin material sheets may alsobe made. Exemplary tubing structures may be in wire form or rod form,with inside diameters ranging from 0.5 mm to 4.0 mm, and wallthicknesses ranging from 0.100 mm to 1.00 mm. “Fine wire” refers to awire having an outer diameter of less than 1 mm.

As used herein, “fatigue strength” refers to the load level at which thematerial meets or exceeds a given number of load cycles to failure.Herein, the load level is given as alternating strain, as is standardfor displacement or strain-controlled fatigue testing, whereby terms arein agreement with those given in ASTM E606, the entirety of which isincorporated herein by reference.

“Nitinol” is a trade name for a shape memory alloy comprisingapproximately 50 atomic % Nickel and balance Titanium, also known asNiTi, commonly used in the medical device industry for highly elasticmetallic implants.

“Superelastic” material is material which is capable of undergoingstrain exceeding 2% with negligible plastic deformation, such that thematerial is able to return to its original dimension after thedeformation without permanent damage.

“DFT®” is a registered trademark of Fort Wayne Metals Research ProductsCorp. of Fort Wayne, Ind., and refers to a bimetal or poly-metalcomposite wire product including two or more concentric layers of metalsor alloys, typically at least one outer layer disposed over a corefilament formed by drawing a tube or multiple tube layers over a solidmetallic wire core element.

“NiTi oxides,” in the context of binary NiTi alloys, are TixNiyOzparticles that form from TixNiy intermetallics with an oxygen content ofas much as 15 at. %. Oxygen may be present in raw materials used forNiTi creation, or may be drawn from the atmosphere during melting andingot formation. Although the total amount of oxygen in the alloy isvery small (e.g. ˜200 ppm) in most cases, the present inventorsrecognize that oxygen does not dissolve in the NiTi binary alloy, and sobecomes part of intermetallic TixNiy during solidification andstabilizes in the form of TixNiyOz oxide particles. These stabilizedNiTi oxides cannot be dissolved by homogenization and unavoidably existin Ti-rich, Ni-Rich and substantially equiatomic, or equal atomicproportion, binary NiTi alloys. Ternary NiTi alloys, such as TiNiCu andTiNiNb, may also form oxides taking the form of, e.g.,Ti_(X)(Cu,Ni)_(Y)O_(Z) or (Ti,Nb)_(X)Ni_(Y)O_(Z), it being understoodthat these and other ternary oxides may be within the scope of “NiTioxides” as used herein.

“Impurities,” “incidental impurities” and “trace impurities” arematerial constituents present in a material at less than 500 parts permillion or 0.05 wt. % for any given element, except that yttrium is notconsidered an impurity within the context of the present disclosure.

Yttrium Alloyed with Nickel and Titanium

As noted above with respect to FIG. 1A (which is drawn to scale,according to scale 9), oxide inclusions may form within themicrostructure of ingot 1. With the recognition that such inclusions maypotentially adversely affect fatigue life of traditional binary NiTialloys, materials made in accordance with the present disclosure wereproduced and tested to present a solution to such variability and/orenhance the mechanical properties of the material. Specific examples ofsuch materials are described below in the Working Examples.

Surprisingly, including only a small amount of yttrium to form an alloyof nickel-titanium-yttrium (NiTiY) has been found to reduce the numberof oxide inclusions present in the alloy during melting andsolidification, without the use of expensive traditional methods forreducing the amount of oxygen present in and around the alloy. As notedabove, two such expensive traditional methods include using extremelyhigh purity raw material, e.g., 99.9995% pure nickel and 99.9995% puretitanium, and forming the NiTi alloy in an extremely high atmosphericvacuum, e.g., in a pressure below 10⁻² Pa (0.07 mTorr).

By contrast and as further described in detail below and in the WorkingExamples, the present class of NiTiY alloys are at least as effective asthese expensive alternatives, with the use of 99.95% pure nickel, 99.8%pure titanium and a vacuum pressure of about 0.67 Pa (5 mTorr).

Embodiments of the nickel-titanium-yttrium alloy of the presentdisclosure have a chemistry that differs from the conventional chemistryof NiTi alloy. These chemical differences provide an alloy that,although meeting the broad chemistry requirements for medical-grade NiTialloy under ASTM F2063, further includes an amount of yttrium that isnot present in a conventional NiTi alloy. The differences in chemistryin the modified NiTiY alloys to which the present disclosure is directedhave been found to inhibit the formation of undesirable oxide inclusionsin the alloys. This, in turn, improves the ability to process the alloyto bar and wire form and enhances the fatigue resistance of alloy andproducts produced from the alloy.

Moreover, improvements in performance and character of the NiTiY alloysdescribed herein have been observed, corresponding to the significantreduction or elimination of the presence of TixNiyOz oxide inclusions inthe alloys. The properties of the alloy vary depending on theconcentration of yttrium in the alloy.

In addition, carbide inclusions (described above) may be limited in thepresent alloy materials by using “cold wall” methods that do not use agraphite crucible, such as Vacuum Arc Re-melt (VAR), Induction SkullMelt (ISM) or by using levitation melt that uses a water-cooled coppercrucible.

The yttrium concentration in the present NiTiY alloy may be as little as0.01 wt. %, 0.02 wt. % or 0.03 wt. %, and as much as 0.08 wt. %, 0.12wt. % or 0.15 wt. %, or may be any concentration in any range defined byany of the foregoing values. For example, the yttrium concentration inthe present NiTiY alloy may be:

between 0.01 wt. % and 0.02 wt. % yttrium;

between 0.01 wt. % and 0.03 wt. % yttrium;

between 0.01 wt. % and 0.08 wt. % yttrium;

between 0.01 wt. % and 0.12 wt. % yttrium;

between 0.01 wt. % and 0.15 wt. % yttrium;

between 0.02 wt. % and 0.03 wt. % yttrium;

between 0.02 wt. % and 0.08 wt. % yttrium;

between 0.02 wt. % and 0.12 wt. % yttrium;

between 0.02 wt. % and 0.15 wt. % yttrium;

between 0.03 wt. % and 0.08 wt. % yttrium;

between 0.03 wt. % and 0.12 wt. % yttrium;

between 0.03 wt. % and 0.15 wt. % yttrium;

between 0.08 wt. % and 0.12 wt. % yttrium;

between 0.08 wt. % and 0.15 wt. % yttrium; or

between 0.12 wt. % and 0.15 wt. % yttrium.

Moreover, the amount of yttrium used in the present NiTiY alloy may alsobe a function of expected or actual oxygen impurities for feedstockmaterials, with lower Y concentrations being sufficient for relativelymore pure Ni and Ti feedstock materials, and higher concentrationsneeded for relatively less pure Ni and Ti feedstock materials.

In the ternary NiTiY alloy described above, the amounts of nickel andtitanium are roughly equal and form the balance of the alloy. The nickelconcentration in the present NiTiY alloy may be as little as 50 wt. %,52 wt. % or 54.5 wt. %, and as much as 57 wt. %, 58.5 wt. % or 60 wt. %,or may be any concentration in any range defined by any of the foregoingvalues. For example, the nickel concentration in the present NiTiY alloymay be:

between 50 wt. % and 52 wt. %;

between 50 wt. % and 54.5 wt. %;

between 50 wt. % and 57 wt. %;

between 50 wt. % and 58.5 wt. %;

between 50 wt. % and 60 wt. %;

between 52 wt. % and 54.5 wt. %;

between 52 wt. % and 57 wt. %;

between 52 wt. % and 58.5 wt. %;

between 52 wt. % and 60 wt. %;

between 54.5 wt. % and 57 wt. %;

between 54.5 wt. % and 58.5 wt. %;

between 54.5 wt. % and 60 wt. %;

between 57 wt. % and 58.5 wt. %;

between 57 wt. % and 60 wt. %; or

between 58.5 wt. % and 60 wt. %.

Titanium may then form the balance of the alloy. Therefore, titanium maybe any constituency between 39.85 wt. % and 49.99 wt. %, and may formthe balance of any alloy formed from any of the foregoing ranges of Niand Y.

In addition, the present NiTiY material may be further alloyed withother materials as required or desired for various potentialapplications. Examples of further alloying elements within the scope ofthe present disclosure include the following elements in the followingamounts in any combination or permutation, provided, however, thatnickel can only be displaced by the following element(s) to the extentthat a minimum nickel content of 20 wt. % is maintained in the finalalloy:

-   -   Copper between 1 wt. % and 10 wt. %, in lieu of an equal amount        of nickel;    -   Niobium between 1 wt. % and 15 wt. %, in lieu of an equal amount        of titanium;    -   Hafnium between 0.5 wt. % and 50 wt. %, in lieu of an equal        amount of titanium;    -   Zirconium between 0.5 wt. % and 35 wt. %, in lieu of an equal        amount of titanium;    -   Cobalt between 0.1 wt. % and 5 wt. %, in lieu of an equal amount        of titanium, nickel, or a combination of titanium and nickel;    -   Chromium between 0.1 wt. % and 1 wt. %, in lieu of an equal        amount of titanium; and/or    -   Iron between 0.1 wt. % and 10 wt. %, in lieu of an equal amount        of titanium, nickel, or a combination of titanium and nickel.

Turning to FIG. 1B (which is drawn to scale, according to scale 90), amicrostructure of an ingot 10 made of a NiTiY alloy in accordance withthe present disclosure and having a yttrium concentration of 0.04 wt. %is shown in an as-cast condition at a magnification such that the scale90 in the lower-right of the figure shows a length of 20 μm on thesurface (or within the cross-section) of the ingot. As can be seen, theingot 10 includes fine inclusions 50 present within the microstructure30 of the alloy. Intact grain boundaries 70 are also shown. Inclusions50 present in FIG. 1B are smaller in size and volume fraction ascompared to those shown in FIG. 1A.

In particular, inclusions 50 are generally small relative to theresulting wire or other construct formed from ingot 10, even where thewire is a fine wire (e.g., wire 730 or 731 as shown in FIGS. 7A-7D anddescribed in further detail below). In an exemplary embodiment, forexample, inclusions 50 are no larger than 39 μm in any dimension iningot 10 as defined in ASTM F2063, and are no larger than 10 μm in anydimension after ingot 10 has been processed into a hot-rolled coilaccording to ASTM F2063. In one particular exemplary embodiment, thetransverse extent (i.e., measured perpendicular to the longitudinal axisof the wire) of inclusions 50 in cold-drawn wire is less than 2 μm suchthat inclusions 50 have a minimized effect on fatigue endurance of sucha wire. In accordance with these exemplary embodiments, FIG. 1Billustrates that the addition of yttrium in the amount of 0.04 wt. %substantially eliminates the presence of large inclusions 5 (FIG. 1A)from the NiTiY alloy material, and instead includes only small NiTiYinclusions 50, e.g., having an average transverse dimension of about 1μm. The small transverse dimension of inclusions 50 promotes enhancedfatigue life of the alloy 10, particularly when alloy 10 is processedinto fine wire as discussed herein.

Referring to FIG. 2A (which is drawn to scale, according to scale 190),the microstructure of an ingot 100 made of a NiTi alloy in accordancewith the present disclosure and having a yttrium concentration of 0.01wt. % is shown at a magnification such that the scale 190 in thelower-right of the figure shows a length of 40 μm on the surface (orwithin the cross-section) of the ingot. As can be seen, ingot 100includes intact grain boundaries 170 and inclusions 150 present withinthe microstructure 130 of the alloy. As compared to those shown in FIG.1A, inclusions 150 present in FIG. 2A are smaller and represent a lesseroverall volume fraction of the parent material. In particular,inclusions 150 are substantially the same average transverse dimensionas those of FIG. 1B. Inclusions 150 can therefore be expected to have aminimized effect on the fatigue endurance of the alloy due to theiracceptably small sizes and extents, particularly when alloy 100 isprocessed into fine wire as discussed herein.

Turning to FIG. 2B (which is drawn to scale, according to scale 290),the microstructure of an ingot 200 made of a NiTiY alloy in accordancewith the present disclosure having a yttrium concentration of 0.02 wt. %at a magnification such that the scale 290 in the lower-right of thefigure shows a length of 40 μm on the surface (or within thecross-section) of the ingot. As can be seen, ingot 200 has intact grainboundaries 270 and fine inclusions 250 present within the microstructure230 of the alloy. Inclusions 250 are controlled in terms of size andvolume fraction as compared to those shown in FIG. 1A. In particular,inclusions 250 are of substantially the same average transversedimension as those of FIGS. 1A and 1B. Inclusions 250 can therefore beexpected to have a minimized effect on the fatigue endurance of thealloy due to their acceptably small sizes and extents, particularly whenalloy 10 is processed into fine wire as discussed herein.

Referring now to FIG. 2C (which is drawn to scale, according to scale390), the microstructure of an ingot 300 made of a NiTiY alloy inaccordance with the present disclosure having a yttrium concentration of0.16 wt % is shown at a magnification such that the scale 390 in thelower-right of the figure shows a length of 20 μm on the surface (orwithin the cross-section) of the ingot. As can be seen, ingot 300 hasinclusions 350 present within the microstructure 330 of the alloy. Ascompared to inclusions 5 of ingot 1 shown in FIG. 1A, inclusions 350 aresmaller and represent a reduced volume fraction of the material. Inparticular, inclusions 350 are of substantially the same averagetransverse dimension and shape as the inclusions of FIGS. 1B, 2A, and 2Bsuch that inclusions 350 can be expected to have a minimized effect onfatigue performance of the material of ingot 300.

However, cracks 370 are also present along some of the grain boundarieswithin the microstructure 330 of the alloy of FIG. 2C. Cracks 370prevent ingot 300 from being worked into fine forms, e.g. fine wire 730,731 described below. In particular, attempts to work ingot 300 into suchfine forms results in propagation of cracks 370 and/or material failurestemming from cracks 370.

Turning now to FIG. 2D (which is drawn to scale, according to scale490), the microstructure of an ingot 400 made of a NiTiY alloy inaccordance with the present disclosure having a yttrium concentration of0.30 wt. % is shown at a magnification such that the scale 490 in thelower-right of the figure shows a length of 40 μm on the surface (orwithin the cross-section) of the ingot. As can be seen in FIG. 2D, ingot400 has inclusions 450 present within the microstructure 430 of thealloy. Inclusions 450 have substantially the same average transversedimension and shape as the inclusions of FIGS. 1B, 2A, and 2B, such thatinclusions 450 can be expected to have a minimized effect on fatigueperformance of the material ingot 400.

However, cracks 470 are also present along some of the grain boundarieswithin the microstructure 430 of the alloy. Cracks 470, similar tocracks 370 shown in FIG. 2C, prevent ingot 400 from being worked intofine forms, e.g. fine wire 730, 731 described below, without propagationor cracks 470 and/or material failure stemming from cracks 470.

By the foregoing findings, the inventors have determined thatmaintaining the yttrium concentration in a NiTiY alloy within a range of0.01 wt. % to less than 0.16 wt. % (e.g., 0.15 wt. % or lower) providesa reduced average transverse inclusion dimension and a correspondingreduction in overall volume fractions of particles/inclusions, as shownin FIGS. 2A-2C. This beneficial result is achieved while also deterringcracking and minimizing brittleness of the material, thereby preservingthe overall ductility and workability of the resulting alloy ingot.

Conversely, when the yttrium concentration in the NiTiY alloy rises to0.16 wt. % and above, the as-casted ingot becomes too brittle anddevelops cracks, negating any potential for working into fine forms suchas wire having a diameter less than 1 mm. In particular, NiTiY withgreater than 0.16 wt. % yttrium develops cracks 370, 470 as shown inFIGS. 2C and 2D which preclude the use of cold work methods. Althoughthese high yttrium concentrations do result in a reduction in averagetransverse inclusion dimension and volume fraction as compared to abinary NiTi alloy, the overall usefulness of the resulting alloy hasbeen found to be impaired by its brittleness.

As noted above, yttrium can also be utilized with other NiTi based shapememory alloy systems to gain similar benefits to the ternary NiTiYalloys described above. Exemplary quaternary and quinary materialsamenable to the beneficial addition of small amounts (e.g., up to 0.15wt. %) of yttrium include Ni—Ti—Hf—Zr, Ni—Ti—Cr—Co—C, Ni—Ti—Fe—Co,Ni—Ti—Nb, Ni—Ti—Zr, Ni—Ti—Co, Ni—Ti—Cr, and Ni—Ti—Cu.

For example, a comparison of FIGS. 3A and 3B illustrates that a NiTiNballoy can benefit from the use of yttrium in a similar fashion to binaryNiTi as described in detail above. FIG. 3A (which is drawn to scale,according to scale 590), illustrates the microstructure of a controlingot 500 made of a NiTiNb alloy lacking yttrium. The image of FIG. 3Ais shown at a magnification such that the scale 590 in the lower-rightcorner of the figure shows a length of 40 μm on the surface (or withinthe cross-section) of the ingot. As illustrated, ingot 500 includesinclusions 550 within the microstructure 530 of the alloy. Inclusions550 are analogous to inclusions 5 of ingot 1 in that they may beresponsible for large variations in fatigue life of the alloys.

Turning to FIG. 3B (which is drawn to scale, according to scale 690),the microstructure of a NiTiNbY ingot 600 made in accordance with thepresent disclosure is illustrated, in which the ingot 600 has a yttriumconcentration of 0.1 wt. %. The image of FIG. 3B is shown at amagnification such that the scale 690 in the lower-right of the figureshows a length of 40 μm on the surface (or within the cross-section) ofthe ingot. As can be seen, ingot 600 has inclusions 650 present withinthe microstructure 630 of the alloy.

Similar to inclusions 50 of the ternary NiTiY alloy shown FIG. 1B,inclusions 650 of the present quaternary NiTiNbY alloy have a generallysmall size, with an average transverse inclusion dimension substantiallysmaller than inclusions 550 in control ingot 500. Inclusions 650 aresmall enough in the transverse direction to have a minimized effect onfatigue endurance of the material of ingot 600, even if such material isdrawn to a fine wire as described further below. In addition, few or nocracks are evident within the microstructure 630 of ingot 600. Thus, theinventors have found that by adding a small amount of Y, such as 0.1 wt.% Y, to a nominally 47 wt. % Ni, 37 wt. % Ti, and 16 wt. % Nb alloy, theTi oxide inclusions in the yttrium-free alloy (shown in FIG. 3A) can besubstantially eliminated from cast ingots and other parts.

Wire Constructs Including NiTiY

In one exemplary embodiment, NiTiY material made in accordance with thepresent disclosure may be formed into a fine medical-grade wire 730,731, as shown in FIG. 6. This wire 730, 731 may then be formed orintegrated into a medical device, such as by braiding into a stent 700having an overall device diameter D_(S). Wires 730, 731 may each have anouter wire diameter D_(W) of less than, e.g., 1 mm.

An alloy in accordance with the present disclosure may first be formedin bulk, such as by traditional casting methods. This bulk material isthen formed into a suitable pre-form material (e.g., a rod, plate orhollow tube) by hot-working the bulk material into the desired pre-formsize and shape. For purposes of the present disclosure, hot working isaccomplished by heating the material to an elevated temperature aboveroom temperature and performing desired shaping and forming operationswhile the material is maintained at the elevated temperature. Theresulting pre-form material, such an ingot, is then further processedinto an intermediate form, such as a rod, wire, tube, sheet or plateproduct by repetitive cold-forming and annealing cycles.

This intermediate material may be made by, for example, a schedule ofdrawing and annealing to create an initial coarse wire structure readyfor final processing. Thereafter, wires 730 or 731 (FIGS. 6 and 7A-7D)may be subjected to a final cold work conditioning step, and possibly afinal heat treatment step, in order to impart desired mechanicalproperties to the finished wire product as further described below.

In one exemplary embodiment shown in FIG. 7A, monolithic wire 731 madeof a NiTiY material (including ternary NiTiY as well as other alloysthereof) may be initially produced using conventional methods, includinga schedule of drawing and annealing in order to convert the pre-formmaterial (such as an ingot or rod) into a wire of a desired diameterprior to final processing. That is, the pre-form material is drawnthrough a die 736 (FIG. 7A) to reduce the outer diameter of theintermediate material slightly while also elongating the material, afterwhich the material is annealed to relieve the internal stresses (i.e.,retained cold work) imparted to the material by the drawing process.This annealed material is then drawn through a new die 736 with asmaller finish diameter to further reduce the diameter of the material,and to further elongate the material. Further annealing and drawing ofthe material is iteratively repeated until the material is formed into awire construct ready for final processing into wire 731.

To form composite wire 730 (FIG. 7B) such as DFT®, core 734 is insertedwithin shell 732 to form an intermediate construct, and an end of thisintermediate construct is then tapered to facilitate placement of theend into a drawing die 736 (FIG. 7B). The end protruding through thedrawing die 736 is then gripped and pulled through the die 736 to reducethe diameter of the construct and bring the inner surface of shell 732into firm physical contact with the outer surface of core 734. Moreparticularly, the initial drawing process reduces the inner diameter ofshell 732, such that shell 732 closes upon the outer diameter of core734 and the inner diameter of shell 732 equals the outer diameter ofcore 734 whereby, when viewed in section, the inner core 734 willcompletely fill the outer shell 732 as shown in FIG. 7B.

Exemplary composite wires 730 may be formed using a NiTiY alloy made inaccordance with the present disclosure (including ternary NiTiY as wellas other alloys thereof) for shell 732 and either platinum (Pt) ortantalum (Ta) for core 734. Addition of such materials contributes tothe radio-opacity, or visibility under x-ray, of nitinol in fine wireform.

The step of drawing subjects wire 730 or 731 to cold work. For purposesof the present disclosure, cold-working methods effect materialdeformation at or near room temperature, e.g. 20-30° C. In the case ofcomposite wire 730, drawing imparts cold work to the material of bothshell 732 and core 734, with concomitant reduction in thecross-sectional area of both materials. The total cold work imparted towire 730 or 731 during a drawing step can be characterized by thefollowing formula (I):

$\begin{matrix}{{cw} = {1 - {\left( \frac{D_{2}}{D_{1}} \right)^{2} \times 100\%}}} & (I)\end{matrix}$

wherein “cw” is cold work defined by reduction of the original materialarea, “D_(2S)” is the outer cross-sectional diameter of the wire afterthe draw or draws, and “D_(1S)” is the outer cross-sectional diameter ofthe wire prior to the same draw or draws.

Referring to FIGS. 7A and 7B, the cold work step may be performed by theillustrated drawing process. As shown, wire 730 or 731 is drawn througha lubricated die 736 having an output diameter D_(2S), which is lessthan diameter Dis of wire 730 or 731 prior to the drawing step. Theouter diameter of wire 730 or 731 is accordingly reduced frompre-drawing diameter Dis to drawn diameter D_(2S), thereby impartingcold work cw.

Alternatively, net cold work may be accumulated in wire 730 or 731 byother processes such as cold-swaging, rolling the wire (e.g., into aflat ribbon or into other shapes), extrusion, bending, flowforming, orpilgering. Cold work may also be imparted by any combination oftechniques including the techniques described here, for example,cold-swaging followed by drawing through a lubricated die finished bycold rolling into a ribbon or sheet form or other shaped wire forms. Inone exemplary embodiment, the cold work step by which the diameter ofwire 730 is reduced from D_(1S) to D_(2S) is performed in a single drawand, in another embodiment, the cold work step by which the diameter ofwire 730 is reduced from D_(1S) to D_(2S) is performed in multiple drawswhich are performed sequentially without any annealing steptherebetween. When calculating cold work cw using formula (I) above, itis assumed that no anneal has been performed subsequent to the processof imparting cold work to the material.

For processes where the drawing process is repeated without anintervening anneal on composite wire 730, each subsequent drawing stepfurther reduces the cross section of wire 730 proportionately, such thatthe ratio of the sectional area of shell 732 and core 734 to the overallsectional area of wire 730 is nominally preserved as the overallsectional area of wire 730 is reduced. Referring to FIG. 7B, the ratioof pre-drawing core outer diameter D_(1C) to pre-drawings shell outerdiameter Dis is the same as the corresponding ratio post-drawing. Statedanother way, D_(1C)/D_(1S)=D_(2C)/D_(2S).

Thermal stress relieving, otherwise known in the art as annealing, at anominal temperature not exceeding the melting point of the wire material(or, for a composite wire, either the first or second materials), isused to improve the ductility of the fully dense composite betweendrawing steps, thereby allowing further plastic deformation bysubsequent drawing steps. Further details regarding wire drawing arediscussed in U.S. Pat. No. 7,989,703, issued Aug. 2, 2011, entitled“Alternating Core Composite Wire”, assigned to the assignee of thepresent invention, the entire disclosure of which is incorporated byreference herein.

Heating wire 730 to a temperature sufficient to cause recrystallizationof grains eliminates accumulated cold work. The cold work imparted byeach iterative cold work process is relieved by fully annealing thematerial between draws, thereby enabling the next iterative cold workingprocess. In full annealing, the cold-worked material is heated to atemperature sufficient to substantially fully relieve the internalstresses stored in the material, thereby relieving the stored cold workand “resetting” cold work to zero.

On the other hand, wires 730 or 731 subject to drawing or othermechanical processing without a subsequent annealing process retain anamount of cold work. The amount of retained work depends upon theoverall reduction in diameter from Dis to Das, and may be quantified onthe basis of individual grain deformation within the material as aresult of the cold work imparted. Referring to FIG. 7C, for example,wire 731 is shown in a post-annealing state, with grains 12 shownsubstantially equiaxed, i.e., grains 12 define generally spheroid shapesin which a measurement of the overall length G1 of grain 12 issubstantially the same regardless of the direction of measurement. Afterdrawing wire 731 (as described above), equiaxed grains 12 are convertedinto elongated grains 14 (FIG. 7D), such that grains 14 are longitudinalstructures defining an elongated grain length G2 (i.e., the longestdimension defined by grain 14) and a grain width G3 (i.e., the shortestdimension defined by grain 14). The elongation of grains 14 results fromthe cold working process, with the longitudinal axis of grains 14generally aligned with the direction of drawing, as illustrated in FIG.7D.

The retained cold work of wire 731 after drawing can be expressed as theratio of the elongated grain length G2 to the width G3, such that alarger ratio implies a grain which has been “stretched” farther andtherefore implies a greater amount of retained cold work. By contrast,annealing wire 731 after an intermediate drawing process recrystallizesthe material, converting elongated grains 14 back to equiaxed grains 12and “resetting” the retained cold work ratio to 1:1 (i.e., no retainedcold work).

For the present NiTiY materials, full annealing may be accomplished at atemperature about 500-800° C. for at least several seconds for thin wire(i.e., having a small cross-sectional area of between 0.000127 sq. mmand 0.5 sq. mm) to tens of minutes for thicker materials (i.e., having alarger cross-sectional area of between 1 sq. mm and 125 sq. mm).Alternatively, a full anneal can be accomplished with a highertemperature, such as between 700° C. and 1100° C., for a shorter time,such as between several milliseconds and less than 5 minutes, againdepending on cross-sectional area of the material. Of course, arelatively higher temperature annealing process can utilize a relativelyshorter time to achieve a full anneal, while a relatively lowertemperature will typically utilize a relatively longer time to achieve afull anneal. In addition, annealing parameters can be expected to varyfor varying wire diameters, with smaller diameters shortening the timeof anneal for a given temperature. Whether a full anneal has beenaccomplished can be verified in a number of ways as well known in theart, such as microstructural examinations using scanning electronmicroscopy (SEM), mechanical testing for ductility, strength,elasticity, etc., and other methods.

Further discussion of cold working and annealing methods can be found inU.S. Pat. No. 8,840,735, issued Sep. 23, 2014 and entitled FATIGUEDAMAGE RESISTANT WIRE AND METHOD OF PRODUCTION THEREOF, the entiredisclosure of which is hereby incorporated by reference.

The resulting coarse wire material may then be finally processed into afinal form, such as a fine wire suitable for integration into a stent orother medical device. Exemplary wire constructs are described in furtherdetail below.

Wire Properties

Fatigue endurance of the present NiTiY alloys can be enhanced dependingon the concentration of yttrium added to the alloy, as described indetail above. For example, as found in Example 1 below, a NiTiY wire canexhibit a “runout” fatigue life of 10⁷ cycles at a strain amplitude of0.1% in the absence of controllable external factors (e.g.,imperfections in drawing dies leading to microstructural defects, orother production irregularities). For purposes of the presentdisclosure, “runout” fatigue is a number of fatigue cycles beyond whichthe subject material is not expected to experience fatigue failure atany number of additional cycles.

This enhanced fatigue endurance of the present NiTiY wire materialsenables the alloy to be used in in vivo applications such as stents,including vascular (e.g., cardiac) and non-vascular (e.g.,gastrointestinal, urinary) stents. Because alloys used in stents andsimilar in vivo applications may undergo many cycles, the present wireis ideally suited for use in stents implanted in high-flexion areas(i.e., extremities) and other demanding applications.

Material properties of the present NiTiY wire materials other thanfatigue resistance are commensurate with similar binary NiTi materials.The present NiTiY materials are therefore suitable for medical deviceapplications where NiTi is currently used, such as stents, pacing leads,etc.

EXAMPLES

The following non-limiting Examples illustrate various features andcharacteristics of the present invention, which is not to be construedas limited thereto.

In these Examples, exemplary monolithic NiTiY alloy wires in accordancewith the present disclosure were produced, tested and characterized,particularly with regard to material workability and mechanicalstrength.

Mechanical performance was then evaluated for each cold worked samplevia a uniaxial tensile test on an Instron Model 5565 test machineavailable from Instron or Norwood, Mass., USA). More specifically,destructive uniaxial tension testing of the wire materials was used toquantify the ultimate strength, yield strength, axial stiffness andductility of candidate materials, using methods described inStructure-Property Relationships in Conventional and NanocrystallineNiTi Intermetallic Alloy Wire, Journal of Materials Engineering andPerformance 18, 582-587 (2009) by Jeremy E. Schaffer, the entiredisclosure of which is hereby expressly incorporated herein byreference. These tests are run using servo-controlled Instron loadframes in accordance with industry standards for the tension testing ofmetallic materials.

For rotary beam fatigue testing in accordance with the Examples herein,a wire sample is cut to a length of approximately about 118 mm (e.g.,for a 0.33 mm diameter wire), then secured at its axial ends torotatable jaws. The free portion of the wire between the jaws is bent tointroduce a desired tensile strain at the “peak” or outermost portion ofthe bend. Directly opposite this peak of the bend, the wire experiencesa compressive strain equal to the tensile strain, with the nominal valueof both the tensile and compressive strains referred to herein as the“strain amplitude.” The jaws are then rotated in concert (i.e., each jawrotated with the same speed and in the same direction), such that thearea of maximum tensile strain is rotated around the wire “peak” andtransitioned to the area of maximum compressive strain with each180-degree rotation of the jaws and wire. Rotary beam fatigue testing isfurther described in ASTM E2948-14, the entire disclosure of which ishereby expressly incorporated herein by reference.

Example 1

A NiTiY alloy with low Y content was vacuum induction melted and castinto an ingot in the form of a rod having a 2-inch diameter, themicrostructure of which is shown in FIG. 2B. The NiTiY alloy was made inaccordance with the present disclosure and has concentrations of 56.78wt. % Ni, 43.06 wt. % Ti, 0.02 wt. % Y, 0.03 wt. % O, with the balancebeing incidental impurities. The alloy was homogenized at 1000° C. for72 hours and then hot worked to a 0.144 inch diameter rod. It was thencold drawn through standard wire-drawing practices, as described above,to a diameter of 0.0128 inches and annealed at 500° C. for 5 minutes toachieve a super-elastic property. As shown in FIG. 4 (which is drawn toscale, according to scale 790) microstructural analysis of the resultingalloy 3A showed that inclusions 5A had an average transverse dimensionof less than 1 μm.

Rotary beam fatigue testing was carried out on the superelastic wiresample. Thirteen samples of the alloy were tested, and the tests wereconducted at a strain amplitude of 1% and a rotation frequency of 60 Hz.The wire was kept in a bath of purified (via reverse osmosis) water at37° C. and left to cycle until the “runout” level of 10⁷ cycles wasreached or the wire experienced failure, whichever occurred first.Twelve of the thirteen samples reached the “runout” level of 10⁷ cycles.One sample fractured at 2,996,258 cycles (see, e.g., fracture 1A in FIG.5, which is drawn to scale according to scale 990).

The data developed for the alloy in the present Example comparesfavorably with standard (Y-free) NiTi (see Example 2), demonstratingthat the present NiTiY material consistently outperforms binary NiTi infatigue life.

Example 2

A standard binary NiTi alloy having concentrations of 56.23 wt. % Ni,43.75 wt. % Ti, and incidental impurities wire was drawn to a 0.0128inch diameter wire and annealed to achieve a super-elastic property.

Rotary beam fatigue testing was conducted. Ten samples of the alloy weretested, and the tests were conducted at a strain amplitude of 1% and arotation frequency of 60 Hz. The wire was kept in a bath of purified(via reverse osmosis) water at 37° C. and left to cycle until the“runout” level of 10⁷ cycles was reached or the wire experiencedfailure, whichever occurred first. For the ten samples, the mean numberof cycles to reach failure was 18,452 cycles, with a maximum of 21,805cycles and a minimum of 14,936 cycles.

Accordingly, the binary NiTi wires exhibited inferior fatigue resistanceas compared to the NiTiY wires made in accordance with the presentdisclosure.

Example 3

A NiTiY alloy with high Y content was vacuum induction melted and castinto an ingot in the form of a rod having a 2-inch diameter. The NiTiYalloy was made in accordance with the present disclosure and hasconcentrations of 56.74 wt. % Ni, 43.05 wt. % Ti, 0.16 wt. % Y, 0.03 wt.% O, with the balance being incidental impurities. The as-cast ingot,the microstructure of which is shown in FIG. 2C, was brittle, and crackswere apparent in the microstructure. The cracks precluded the alloy frombeing worked into a wire.

Accordingly, the NiTiY wires made with a low concentration of yttrium(i.e., no more than 0.15 wt. %) exhibited superior workability ascompared to the higher-concentration (i.e., 0.16 wt. %) samples.

While this invention has been described as having an exemplary design,the present invention can be further modified within the spirit andscope of this disclosure. This application is therefore intended tocover any variations, uses, or adaptations of the invention using itsgeneral principles. Further, this application is intended to cover suchdepartures from the present disclosure as come within known or customarypractice in the art to which this invention pertains and which fallwithin the limits of the appended claims.

1-6. (canceled)
 7. A nickel-titanium (NiTi) alloy, comprising: at least20 wt. % nickel; between 35 wt. % titanium and 55 wt. % titanium;between 0.01 wt. % yttrium and 0.15 wt. % yttrium; and at least one of:copper between 1 wt. % and 10 wt. %, in lieu of an equal amount ofnickel; niobium between 1 wt. % and 15 wt. %, in lieu of an equal amountof titanium; hafnium between 0.5 wt. % and 50 wt. %, in lieu of an equalamount of titanium; zirconium between 0.5 wt. % and 35 wt. %, in lieu ofan equal amount of titanium; cobalt between 0.1 wt. % and 5 wt. %, inlieu of an equal amount of titanium, nickel, or a combination oftitanium and nickel; chromium between 0.1 wt. % and 1 wt. %, in lieu ofan equal amount of titanium; and iron between 0.1 wt. % and 10 wt. %, inlieu of an equal amount of titanium, nickel, or a combination oftitanium and nickel. 8-11. (canceled)
 12. A method of making anickel-titanium (NiTi) alloy, comprising: providing at least 20 wt. %nickel; providing between 35 wt. % titanium and 55 wt. % titanium;providing between 0.01 wt. % yttrium and 0.15 wt. % yttrium; providingat least one of: copper between 1 wt. % and 10 wt. %, in lieu of anequal amount of nickel; niobium between 1 wt. % and 15 wt. %, in lieu ofan equal amount of titanium; hafnium between 0.5 wt. % and 50 wt. %, inlieu of an equal amount of titanium; zirconium between 0.5 wt. % and 35wt. %, in lieu of an equal amount of titanium; cobalt between 0.1 wt. %and 5 wt. %, in lieu of an equal amount of titanium, nickel, or acombination of titanium and nickel; chromium between 0.1 wt. % and 1 wt.%, in lieu of an equal amount of titanium; and iron between 0.1 wt. %and 10 wt. %, in lieu of an equal amount of titanium, nickel, or acombination of titanium and nickel; and forming an ingot including thenickel, the titanium and the yttrium, the ingot further including atleast one of the copper, the niobium, the hafnium, the zirconium, thecobalt, the chromium and the iron.
 13. The method of claim 12, furthercomprising forming the ingot into a fine wire having a diameter of up to1 mm.
 14. The method of claim 12, further comprising forming the ingotinto an intermediate construct comprising one of a rod, wire, tube,sheet or plate by repetitive cold-forming and annealing cycles.
 15. Themethod of claim 14, further comprising forming the intermediateconstruct into a fine wire having a diameter of up to 1 mm.